CN106459756A - LED package with red-emitting phosphors - Google Patents

LED package with red-emitting phosphors Download PDF

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Publication number
CN106459756A
CN106459756A CN201580031761.6A CN201580031761A CN106459756A CN 106459756 A CN106459756 A CN 106459756A CN 201580031761 A CN201580031761 A CN 201580031761A CN 106459756 A CN106459756 A CN 106459756A
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China
Prior art keywords
adhesive
phosphor
composite bed
composite
microns
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Granted
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CN201580031761.6A
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CN106459756B (en
Inventor
A.A.塞特卢尔
S.E.韦弗
T.B.戈齐卡
A.I.乔德胡里
J.E.墨菲
F.加西亚
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Karent lighting solutions Co.,Ltd.
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/617—Silicates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

The invention discloses a LED package with red-emitting phosphors. According to the invention, a process for fabricating a LED lighting apparatus includes disposing a composite coating on a surafce of a LED chip. The composite coating comprises a first composite layer having a manganese doped phosphor of formula I and a first binder and a second composite layer comprising a second phosphor composition and a second binder. The first binder, the second binder or both include a poIy(meth)acrylate. Ax [MFy]:Mn4+.......... (I), wherein A is Li, Na. K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, AL Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; y is 5, 6 or 7.

Description

There is the LED encapsulation of the phosphor glowing
Background
The such as phosphor described in US the 7358542nd, US 7497973 and US 7648649 based on by Mn4+Activate The phosphor glowing of composite fluoride material can be with such as YAG:Yellow light-emitting low temperature/the green glow of Ce or other garnet ingredients Combination of phosphors and utilize, with realize with by produced by current fluorescent lamp, incandescent lamp and Halogen lamp LED light equivalence from The warm white of blue led（CCT on black body locus<5000 K, color rendition index（CRI）>80）.These materials absorb consumingly Blue light, and, launch efficiently so that little peony/NIR launches between about 610-635 nm.Therefore, with wherein Visual sensitivity is that the red-emitting phosphor of the substantial amounts of transmitting of local in poor more peony is compared, and makes luminous efficacy maximize.? Blue（440-460 nm）Exciting down, quantum efficiency can exceed 85%.
Although using Mn4+Effect of the illuminator of the fluoride matrix (host) of doping and CRI can be at a relatively high, But a potential restriction is that these illuminators are under conditions of use to the sensitiveness degenerated.As described in US 8252613 , it is possible to after use, synthesis process step reduces this degeneration.But, for improving the alternative method of the stability of material Exploitation be desired.
Content of the invention
Briefly, in an aspect, the present invention relates to the process for making LED illumination device, this process include by Composite coating is arranged on the surface of LED chip.Composite coating includes：First composite bed, it has the phosphorescence of the additive Mn of Formulas I Body and the first adhesive；With the second composite bed, it has the second phosphor component and the second adhesive.First adhesive, second Adhesive or both all comprises to gather（Methyl）Acrylate.
Ax[MFy]：Mn4+……（I）
Wherein,
A is Li, Na, K, Rb, Cs or a combination thereof；
M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof；
X is [MFy] absolute value of electric charge of ion；
Y is the 5th, 6 or 7.
In another aspect, the composite coating being arranged in LED chip is included according to the LED illumination device of the present invention.Multiple Close coating to include：First composite bed, its phosphor with the additive Mn of Formulas I and the first adhesive；With the second composite bed, its tool Have the second phosphor component and the second adhesive.First adhesive, second adhesive or both all comprise to gather（Methyl）Acrylic acid Ester.
Brief description
When detailed description below is read with reference to the drawings, by become better understood the present invention these and other special Levy, aspect and advantage, wherein, accompanying drawing in the whole text in, similar character representation similar portion, wherein：
Fig. 1 is the schematic cross section of the lighting apparatus according to the present invention；
Fig. 2 is the schematic cross section through composite coating according to an embodiment of the invention；
Fig. 3 A illustrates the cross section of the configuration of the composite coating being arranged in LED chip according to an embodiment of the invention Figure；
Fig. 3 B illustrates the cross section of the configuration of the composite coating being arranged in LED chip according to another embodiment of the present invention Figure；
Fig. 4 illustrates the emission spectrum of two configurations of the composite coating shown in Fig. 3 A and Fig. 3 B.
Detailed description of the invention
As used in the whole text in specification and claims herein, approximating language can apply to modification can Allow that any quantity of change represents, and be not resulted in the change in the basic function relevant with it.Therefore, by such as " about " A term or multiple term and the value changed is not limited to specified accurate value.In some instances, approximating language can With with for corresponding to the precision of the instrument that this value measures.In following specification and claims, odd number shape Formula " one ", " one " and " being somebody's turn to do " include multiple object, unless context is expressly otherwise indicated.
Unless otherwise defined, otherwise technical term used herein and scientific terminology have and by neck belonging to the present invention The identical implication of implication that the technical staff in territory understands at large.As used herein, term " first ", " second " etc. are no Represent any order, quantity or importance, but and be used to distinguish an element with another.
In the disclosure, when layer is described as " on another layer or substrate ", it is understood that layer can connect directly to each other Touch, or there is being positioned between layer（Or it is multiple）Layer or feature.And, term " ... on " describing layer each other relative Position, and, it is not necessary to mean " ... on ", because the relative position above or below, depends on device for sight The orientation of the person of examining.Additionally, for convenience, the modification of " top ", " bottom ", " top ", " lower section " and these terms is carried out Use, and do not require any specific orientation of assemblies, unless otherwise prescribed." adjacent " meaning as used herein, the term Taste two layers and is continuously provided and is in direct contact with one another.
Figure 1 illustrates lighting apparatus according to an embodiment of the invention or the cross section of luminescent composition part or lamp 10 Figure.Lighting apparatus 10 includes being shown as light emitting diode（LED）The semiconductor radiant source of chip 12 and be electrically attached to LED chip Lead-in wire 14.Lead-in wire 14 can be the thin wire being supported by one or more thicker lead frames 16, or lead-in wire can be voluntarily The electrode supporting, and it is possible to omit lead frame.Lead-in wire 14 supplies current to LED chip 12, and thus makes LED core Piece 12 launches radiation.
Lamp can include any semiconductor blue or UV light source, and it is when its radiation launched is directed on phosphor, energy Enough produce white light.In one embodiment, semiconductor light source is the blue light-emitting LED doped with various impurity.An embodiment In, LED can be containing at least one semiconductor layer comprising GaN, ZnSe or SiC.Specifically, semiconductor light source can be to have More than about 250 nm and less than about 550 nm transmitting wavelength based on Formulas I niGajAlkN（Wherein, 0≤i；0≤j；0 ≤ k, and, I+j+k=1）The blue light-emitting LED semiconductor diode of nitride-based semiconductor.More specifically, LED chip 12（Fig. 1）Can be the nearly UV or blue light-emitting LED of the peak emission wavelength with from about 400 to about 500 nm.In ability Known this kind of LED semiconductor in territory.For convenience, herein, radiation source is described as LED.But, as used herein , term means to include all of semiconductor radiant source including such as semiconductor laser diode.Although additionally, herein The general discussion of the exemplary structure of the present invention being discussed for the light source based on inorganic LED, it is to be understood that, LED core Piece can be replaced by another radiation source, unless be also noted that, and any draws semiconductor semiconductor LED or LED chip With only representing any suitable radiation source, including but not limited to Organic Light Emitting Diode.
In lighting apparatus 10, composite coating 22 is arranged on the surface of LED chip 12.Composite coating 22 includes that first is multiple Closing layer and the second composite bed, each composite bed has at least one phosphor component.In an example, phosphor component and LED Chip 12 couples in the way of radiating.Couple it is meant that element is associated with each other in the way of radiation so that will be from a unit The radiation-emitting of part is to another element.For example, composite coating 22 is arranged in LED chip 12, for example will be from LED chip 12 Radiation-emitting to phosphor, and, the radiation of the different wavelength of phosphor emission.
In the particular embodiment, LED chip 12 is blue led, and, the first composite bed includes that the red line of Formulas I is launched Phosphor, and, the second composite bed includes yellowish green phosphor, the yttrium-aluminium-garnet Ce of such as cerium dopping:YAG.By LED The blue light that chip 12 is launched is mixed by the ruddiness and green-yellow light of the first composite bed and the phosphor emission of the second composite bed with respectively Close, and, obtained transmitting（Indicated by arrow 24）Show as white light.
LED chip 12 can be surrounded by sealant material 20.As known in the art, sealant material 20 is permissible It is low temperature glass or thermoplasticity or thermosetting polymer or resin, for example, silicone or epoxy resin.LED chip 12 and sealant Material 20 can be packaged in shell 18.Shell 18 and sealant 20 should be both transparent, to allow by those elements Launch white light 24.In certain embodiments, sealant material can form shell 18.In addition, scattering particles can be with embedding sealing agent In material.Scattering particles can be such as aluminum oxide or titanium dioxide.Scattering particles preferably have with the negligible quantity of absorption Make to effect the direction light scattering launched from LED chip.
In alternative embodiment, lamp 10 can only include sealant material, and does not have shell 18.LED chip 1 is permissible For example by lead frame the 16th, by the electrode of self-supported, shell 18 bottom or by the pedestal being installed to shell 18 or lead frame（Not Illustrate）Support.
The manganese of Formulas I（Mn4+）The phosphor of doping is the manganese that red line is launched（Mn4+）The composite fluoride phosphor of doping.? In the context of the present invention, term " composite fluoride material or phosphor " means containing at least one coordination center, is filled When the fluorine ion cincture of part and if desired by the complex of counter ion charge compensation.Example K2SiF6:Mn4+ In, coordination center is Si, and, counter ion is K.Composite fluoride writes the combination for single binary fluoride once in a while, but this Represent the ligancy of the part not indicated around coordination center.Square brackets（Once in a while in order to simply omit）Indicate what they were included Complex ion is the new chemical species different from single fluorine ion.Activator ion（Mn4+）Act also as coordination center, substitute matrix brilliant The part of center of a lattice, such as Si.Parent lattice（Including counter ion）Exciting and sending out of activator ion can be changed further Penetrate character.
In the particular embodiment, the coordination center of phosphor, i.e. the M in Formulas I, is Si, Ge, Sn, Ti, Zr or its group Close.More specifically, coordination center is Si, Ge, Ti or a combination thereof, and, the A in counter ion or Formulas I be Na, K, Rb, Cs or its Combination, and, y is 6.The example of the precursor of Formulas I includes K2[SiF6]:Mn4+、K2[TiF6]:Mn4+、K2[SnF6]:Mn4+、Cs2 [TiF6]:Mn4+、Rb2[TiF6]:Mn4+、Cs2[SiF6]:Mn4+、Rb2[SiF6]:Mn4+、Na2[TiF6]:Mn4+、Na2[ZrF6]: Mn4+、K3[ZrF7]:Mn4+、K3[BiF6]:Mn4+、K3[YF6]:Mn4+、K3[LaF6]:Mn4+、K3[GdF6]:Mn4+、K3[NbF7]: Mn4+、K3[TaF7]:Mn4+.In the particular embodiment, the precursor of Formulas I is K2SiF6:Mn4+.
In one embodiment, Mn4+The phosphor of doping is selected from by the group constituting as follows：
（A）A2[MF5]:Mn4+, wherein, A selected from Li, Na, K, Rb, Cs with and combinations thereof；Further, wherein, M is selected from Al, Ga, In With and combinations thereof；
（B）A3[MF6]:Mn4+, wherein, A selected from Li, Na, K, Rb, Cs with and combinations thereof；Further, wherein, M is selected from Al, Ga, In With and combinations thereof；
（C）Zn2[MF7]:Mn4+, wherein, M selected from Al, Ga, In with and combinations thereof；
（D）A[In2F7]:Mn4+, wherein, A selected from Li, Na, K, Rb, Cs with and combinations thereof；
（E）A2[MF6]:Mn4+, wherein, A selected from Li, Na, K, Rb, Cs with and combinations thereof；Further, wherein, M selected from Ge, Si, Sn, Ti, Zr with and combinations thereof；
（F）E[MF6]:Mn4+, wherein, E selected from Mg, Ca, Sr, Ba, Zn with and combinations thereof；Further, wherein, M selected from Ge, Si, Sn, Ti, Zr with and combinations thereof；
（G）Ba0.65Zr0.35F2.70:Mn4+；And
（H）A3[ZrF7]:Mn4+, wherein, A selected from Li, Na, K, Rb, Cs with and combinations thereof.
Based on the gross weight of precursor or phosphor, Formulas I and group（A）-（H）Mn4+The precursor neutralized reaction product phosphor of doping In the amount of manganese from about 0.3 weight %（wt%）To about 2.5 wt%（From about 1.2 moles of %（mol%）To about 10 mol%） Variation.In certain embodiments, the amount of manganese is from about 0.3 wt% to about 1.5 wt%（From about 1.2 mol% to about 6 mol%）Variation, specifically, from about 0.50 wt% to about 0.85 wt%（From about 2 mol% to about 3.4 mol%）Become Dynamic, and more specifically, from about 0.65 wt% to about 0.75 wt%（From about 2.6 mol% to about 3 mol%）Variation. In other embodiments, the amount of manganese is from about 0.75 wt% to about 2.5 wt%（About 3 mol% to about 10 mol%）Become Dynamic, specifically, from about 0.9 wt% to about 1.5 wt%（From about 3.5 mol% to about 6 mol%）Variation, more specifically Ground, from about 0.9 wt% to about 1.4 wt%（About 3.0 mol% to about 5.5 mol%）Variation, and, even more specifically Ground, from about 0.9 wt% to about 1.3 wt%（About 3.5 mol% to about 5.1 mol%）Variation.
Mn4+The phosphor of doping can have containing with the D50 in the scope from about 10 microns to about 80 microns The particle population of the particle size distribution of value.Phosphor material described herein is commercially available, or by such as The method being known in the art, for example via by combination for example as the oxide of raw-material element, carbonate and/or The solid phase reaction method of hydroxide and prepare.In some embodiments it will be desirable to D50 of e.g., less than about 30 microns The particle of the big malo granular size of grain.In the particular embodiment, the D50 granular size of particle is from about 10 microns to greatly About 20 microns of variations, and more specifically, the variation from about 12 microns to about 18 microns.In certain embodiments, such as the U.S. Described in patent No.8252613, to Mn4+The particle of the phosphor of doping carries out post-processing for improving obtained phosphorus The performance of body of light and colour stability.
Fig. 2 is composite coating 22（Also referred to as " laminate "）Cross-sectional view, this illustrates composite coating 22 by least Two-layer forms:First composite bed 34 and the second composite bed 36.First composite bed 34 includes the phosphor and first of the additive Mn of Formulas I Adhesive.Second composite bed 36 includes the second phosphor（Additional phosphor）With the second adhesive.Second phosphor is to launch With the first composite bed 34 and LED chip 12（Fig. 1）Launch combination and produce the phosphor component of the radiation of white light, hereinafter This is described in detail.
In one embodiment, phosphor component intersperses among in the adhesive material in composite bed.Phosphor can be made to become Divide and adhesive material（Or adhesive）Mixing forming composite phosphor material, be then able to pressing composite phosphor material with Form composite bed or film.Composite phosphor material can include phosphor component and the gluing as matrix taking the form of powder Mixture material.Matrix or adhesive material can be sealant materials.The suitable example of adhesive material can be as at this Low temperature glass known in the art or thermoplasticity or thermosetting polymer or resin, for example, silicone or epoxy resin.
In one embodiment, phosphor and the mixing of the first adhesive of Formulas I are made, and, carry out heating simultaneously to mixture And pressing, to form the first composite bed 34.In one embodiment, the second phosphor and the mixing of the second adhesive are made；And so After, heat and press, to form the second composite bed 36.First adhesive and the second adhesive both should to from LED and phosphor emission just transparent.In one embodiment, the first adhesive, the second adhesive or both all have The higher glass transition temperature of operation temperature than LED chip（Tg）.According to one embodiment of present invention, the first bonding Agent, the second adhesive or both are all poly-（Methyl）Acrylate polymer or copolymer.Suitable poly-（Methyl）Acrylate Adhesive is including but not limited to poly-（Methyl methacrylate）（PMMA）.From（Methyl）Acrylic acid and（Methyl）Acrylate monomer The preparation of derivative many polymer and copolymer may be used for adhesive.In certain embodiments, the first adhesive and second Adhesive is both（Methyl）Acrylate.In certain embodiments, the second adhesive can be the material with the first adhesive Expect different materials.The suitable example of different adhesive materials can include but is not limited to from such as Merlon, cyclenes Single polymers of the material acquisition of hydrocarbon, polysulfones, polyester, polystyrene, polypropylene and fluoroplastics resin and copolymer.
In certain embodiments, adhesive material（First adhesive or the second adhesive）There is refractive index R, and, contain There is the diluent materials having less than about 5% absorbance and the refractive index of R ± 0.1.Diluent materials has≤1.7, tool Body ground≤1.6, and more specifically≤1.5 refractive index.In the particular embodiment, diluent materials is formula Ax[MFy], and And, there is the refractive index of about 1.4.Optically inactive material is added to phosphor/binder combination to produce and passes through phosphorescence The milder distribution of the luminous flux of body/sealant blends, further, it is possible to cause the damage less to phosphor.For dilute The suitable material releasing agent includes having from about 1.38（AlF3And K2NaAlF6）To about 1.43（CaF2）The refractive index of variation Such as LiF, MgF2、CaF2、SrF2、AlF3、K2NaAlF6、KMgF3、CaLiAlF6、K2LiAlF6And K2SiF6Fluorine compounds (fluoride compound) and the polymer with from about 1.254 to about 1.7 refractive indexes changing.It is adapted for use as The nonrestrictive example of the polymer of diluent includes Merlon, polyester, nylon, PEI, polyether-ketone and from benzene Ethene, acrylate, methacrylate, vinyl, vinylacetate, ethene, expoxy propane and oxirane monomers derive Polymer and its copolymer, it includes halide derivative and non-halogenated derivative.Before curing these can be polymerized Thing powder is directly incorporated into the adhesive material of such as acrylate.
During pressing, heat composite phosphor material at least to its corresponding melt temperature always.An enforcement In example, heating-up temperature can be from about 150oC to about 200oC changes.When heating, adhesive material softens；Further, phosphorescence Body material dispersion is in corresponding melted adhesive, to form the first composite bed 34 and the second composite bed 36 respectively.
Subsequently, the layer (the first composite bed 34 and the second composite bed 36) these being individually formed with one another it On mode arrange and bond, to form laminate or composite coating 22.In one embodiment, the first composite bed 34 is basic Upper covering the second composite bed 36 so that one layer of light launched in layer is passed through another layer.In certain embodiments, lamination is made Plate solidifies, with by two layer bondings.During curing, adhesive material spreads in the interface of two layers 34 and 36, and, Form binding part between two layers（Joint）.Alternatively, adhesive can be used for two layer connections.Then, by obtained Laminate or composite coating 22 be arranged in LED chip 12.In some instances, polymeric layer or layer of silicone（Not shown）Energy Enough composite coating 32 is adhered to chip.In certain embodiments, to be remotely arranged in LED chip 12 attached for composite coating 22 Closely.
Laminate or composite coating can be molded in different shapes, and it can directly be positioned in board-like encapsulation Or can be cut into square on LED and be positioned in LED encapsulation.One embodiment is the encapsulation of chip-scale.
As mentioned above, phosphor material（Take the form of powder）Intersperse among the adhesive material in composite bed In.Adhesive material in phosphor can intersperse among the single region of this layer or specific region or in this layer whole In volume.By selecting the particulate of the adhesive material of suitable granular size, can to phosphor material in this layer point Cloth is controlled.The particulate of adhesive material can have with the particle size distribution of the D50 value less than about 300 microns.? In one embodiment, particulate has the D50 granular size in the scope from about 150 microns to about 300 microns.At one In embodiment, the less particulate for example with the D50 granular size less than about 50 microns is desired.An embodiment In, binder particles has the D50 granular size in from about 20 microns to about 50 micrometer ranges.
The granular size of adhesive material can be customized, to adjust the spacing between the phosphor particles in composite bed.Make The height forward direction of the light that may result in the big spacing between phosphor particles and LED emission by big binder particles size dissipates Penetrate.This can be similar at a temperature of the melt temperature of adhesive to make phosphor mix with adhesive realize.Due to polymerization The viscosity of thing is high at such a temperature, thus almost without the dispersion of generation phosphor particles（Mixing or precipitation）.Use little Adhesive particle size may result in the phosphor particles closely filled and the relatively low forward scattering with high-selenium corn.
Refer again to Fig. 1, the blue light launched by LED chip 12 with by the first composite bed 34 and second of composite coating 22 Composite bed 36（Fig. 2）The light mixing launched, and, mixed light shows as white light.By to first and second phosphor Particle（As discussed above）Granular size and/or distribution be controlled, thus by adhesive material or both Before being all pressed in the first composite bed 34 and the second composite bed 36, the light from indivedual layers can be launched and be tuned, with Produce expected color dot.
In addition, by the position of the first phosphor and the second phosphor is controlled（More from LED chip 12 closer to or more Far）Such that it is able to light is launched be tuned further.Fig. 3 A and Fig. 3 B illustrates through having be arranged on chip 12 compound The cross-sectional view of the LED chip 12 of coating 22, thus describe two configurations.In figure 3 a, composite coating 22 is arranged at LED chip On 12, competing cause to be positioned to the first composite bed 34 of the phosphor of the additive Mn containing Formulas I close to（Adjacent to）LED chip 12.I.e., in the configuration, composite coating 22 is arranged in LED chip 12, and wherein the first composite bed 34 side is arranged on chip. In figure 3b, composite coating 22 is arranged in LED chip 12, and wherein the second composite bed 36 is arranged adjacently to（Downwards）LED core Piece 12, and, the first composite bed 34 side（Containing PFS）It is arranged to further from LED chip 12.For example, Fig. 4 and Biao 1 illustrates two The spectral characteristic of LED-based lamp, a lamp is arranged at the layer side containing PFS on chip（PFS is downward）, and, another Lamp is arranged at the layer side containing YAG on chip（YAG is downward）.Hereinafter, on the cross section of example, these are described in detail Exemplary lamp and corresponding result.
Additionally, as described in the U.S. Patent Application Serial Number 14/073141 submitted on November 6th, 2013, contain The first composite bed 34 having the phosphor of Formulas I can have the classification composition of the phosphor of Formulas I.The composition of the phosphor of Formulas I across In the granular size of its thickness (that is, on the orthogonal direction of the plane on the surface with LED chip 12) or manganese concentration, grain density One or more middle change.In one embodiment, minimum of a value from the region close to LED chip 12 for the manganese concentration to Maximum value in the relative region of LED chip 12.In one embodiment, the density of the particle of the first population is more than second The density of the particle of population.In one embodiment, the D50 granular size of the first population of particle is more than the second population of particle D50 granular size.
Phosphor particles can be set with banded structure, and wherein, the particle of the first population is usually located at the first composite bed In the region close to LED chip of 34, and, the particle of the second population is usually located in the region relative with LED chip.? In some examples, the first composite bed 34 includes two the single layers arranging in the way of on another；One layer There is the particle of the first population, and, another layer has the particle of the second population.It is unexpected that first composite bed 34 can not have composition The different interface of ground change.The particle of the second population in can making the particle of the first group and the first composite bed 34 in the whole text mixes Close；But, in all of these embodiments, layer 34 has in one of manganese concentration, grain density or granular size or many The classification composition of individual change.
Root is it is contemplated that the second phosphor in LED chip and the second composite bed 36 and Mn4+Doping combination of phosphors and produce The raw obtained transmitting with color dot, colour temperature or colour rendering.With the radiation in the scope launching about 250 to 550 nm Blue or nearly UV LED combination and for, when in lighting apparatus, being white light by the obtained light that sub-assembly is launched.Second phosphorus Body of light can include can with the combination of phosphors of Formulas I and for the white of the light obtained by customizing and produce specific spectrum The green of power distribution, yellow, blueness, redness, the phosphor of orange or other colors.In some instances, respectively include at least Multiple composite beds of one phosphor component can be used to form composite coating.
The phosphor material of green light or gold-tinted can include that europium adulterates or the rare earth oxide of cerium dopping or oxynitride One or more of phosphor.More specifically, the second phosphor is when being excited by LED chip, launch the phosphorescence of green-yellow light The YAG (Y, Gd, Tb, La, Sm, Pr, Lu) of body, such as Ce doping3(Al,Ga)5-xO12-3/2x:Ce3+（Wherein, 0≤x≤0.5）.
For including but is not limited to following phosphor with other suitable phosphor that the phosphor of Formulas I is used together：
((Sr1-z(Ca,Ba,Mg,Zn)z)1-(x+w)(Li,Na,K,Rb)wCex)3(Al1-ySiy)O4+y+3(x-w)F1-y-3(x-w), 0<x≤ 0.10,0≤y≤0.5,0≤z≤0.5,0≤w≤x；
(Ca,Ce)3Sc2Si3O12(CaSiG)；
(Sr,Ca,Ba)3Al1-xSixO4+xF1-x:Ce3+(SASOF))；
(Ba,Sr,Ca)5(PO4)3(Cl,F,Br,OH):Eu2+, Mn2+；
(Ba,Sr,Ca)BPO5:Eu2+, Mn2+；
(Sr,Ca)10(PO4)6*νB2O3:Eu2+（Wherein, 0<ν≤1）；
Sr2Si3O8*2SrCl2:Eu2+；
(Ca,Sr,Ba)3MgSi2O8:Eu2+, Mn2+；
BaAl8O13:Eu2+；
2SrO*0.84P2O5*0.16B2O3:Eu2+；
(Ba,Sr,Ca)MgAl10O17:Eu2+, Mn2+；
(Ba,Sr,Ca)Al2O4:Eu2+；
(Y,Gd,Lu,Sc,La)BO3:Ce3+, Tb3+；
ZnS:Cu+, Cl-；
ZnS:Cu+, Al3+；
ZnS:Ag+, Cl-；
ZnS:Ag+, Al3+；
(Ba,Sr,Ca)2Si1-ξO4-2ξ:Eu2+（Wherein, 0.2≤ξ≤0.2）；
(Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+；
(Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+；
(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+（Wherein, 0≤α≤0.5）；
(Ca,Sr)8(Mg,Zn)(SiO4)4Cl2:Eu2+, Mn2+；
Na2Gd2B2O7:Ce3+, Tb3+；
(Sr,Ca,Ba,Mg,Zn)2P2O7:Eu2+, Mn2+；
(Gd,Y,Lu,La)2O3:Eu3+, Bi3+；
(Gd,Y,Lu,La)2O2S:Eu3+, Bi3+；
(Gd,Y,Lu,La)VO4:Eu3+, Bi3+；
(Ca,Sr)S:Eu2+, Ce3+；
SrY2S4:Eu2+；
CaLa2S4:Ce3+；
(Ba,Sr,Ca)MgP2O7:Eu2+, Mn2+；
(Y,Lu)2WO6:Eu3+, Mo6+；
(Ba,Sr,Ca)βSiγNμ:Eu2+（Wherein, 2 β+4 γ=3 μ）；
(Ba,Sr,Ca)2Si5-xAlxN8-xOx:Eu2+（Wherein, 0≤x≤2）；
Ca3(SiO4)Cl2:Eu2+；
(Lu,Sc,Y,Tb)2-u-vCevCa1+uLiwMg2-wPw(Si,Ge)3-wO12-u/2（Wherein ,-0.5≤u≤1,0<V≤0.1, and And 0≤w≤0.2）；
(Y,Lu,Gd)2-φCaφSi4N6+φC1-φ:Ce3+,（Wherein, 0≤φ≤0.5）；
(Lu, Ca, Li, Mg, Y), doped with Eu2+And/or Ce3+α-SiAlON；
(Ca,Sr,Ba)SiO2N2:Eu2+, Ce3+；
β-SiAlON：Eu2+, 3.5MgO*0.5MgF2*GeO2:Mn4+；
(Sr,Ca,Ba)AlSiN3:Eu2+；
(Sr,Ca,Ba)3SiO5:Eu2+；
Ca1-c-fCecEufAl1+cSi1-cN3（Wherein, 0≤c≤0.2,0≤f≤0.2）；
Ca1-h-rCehEurAl1-h(Mg,Zn)hSiN3（Wherein, 0≤h≤0.2,0≤r≤0.2）；
Ca1-2s-tCes(Li,Na)sEutAlSiN3（Wherein, 0≤s≤0.2,0≤f≤0.2, s+t>0）；And
Ca1-σ-χ-φCeσ(Li,Na)χEuφAl1+σ-χSi1-σ+χN3（Wherein, 0≤σ≤0.2,0≤χ≤0.4,0≤φ≤0.2）.
The other materials being suitable for using with the combination of phosphors in composite coating 32 can include such as polyfluorene, preferably Ground, poly-（9,9-dioctyl fluorene）Electroluminescent polymer and copolymer, for example poly-（Double-the N of 9,9 '-dioctyl fluorene-co-, N'-（4-butyl phenyl）Diphenylamines）（F8-TFB）；Poly-（VCz）With polyphenylene vinylene and derivative thereof.Separately Outward, luminescent layer can include blueness, yellow, orange, green or red phosphorescent dye or metal complex or a combination thereof.It is suitable for Material as phosphorescent coloring includes but is not limited to three（1-phenyl isoquinolin quinoline）Iridium（III）（Orchil）, three（2-phenyl pyrazoline Pyridine）Iridium（Green colouring material）And iridium（III）Double（2-（4,6-difluorophenyl）Pyridine (pyridinato)-N, C2）（Blue dye Material）.Can also use from ADS（American dye source limited company）The fluorescence being commercially available and phosphorescence gold Belong to complex compound.ADS green colouring material include ADS060GE, ADS061GE, ADS063GE and ADS066GE, ADS078GE and ADS090GE.ADS blue dyes includes ADS064BE, ADS065BE and ADS070BE.ADS orchil includes ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077RE.
Generally, in the composite bed with essentially homogeneously scattered phosphor particles, by the radiation of phosphor emission The gross mass of the phosphor in depending on composite bed with the total amount of the LED radiation absorbing.If in constant surface area A and thickness In the composite bed of degree T, the quality of phosphor is M, then in one embodiment, and density M/ of phosphor（AT）From about 0.10 g/cm3To about 1.5 g/cm3Variation.Additionally, density can be from about 0.25 g/cm3To about 0.75 g/cm3Scope In.
Generally, individual other phosphor（The phosphor of Formulas I and the second phosphor）In the ratio of each and at composite coating In dispersion can be depending on expected light output characteristic and change.Can be to the phase of the individual other phosphor in various embodiments Comparative example is adjusted so that when the transmitting making an other phosphor in LED light device is mixed and is used, produce Predetermined on raw CIE chromaticity diagramxValue andyThe visible ray of value.As discussed, preferably produce white light.White light can for example can be gathered around Have in the scope of about 0.30 to about 0.55xIt is worth and in the scope of about 0.30 to about 0.55yValue.As institute State, but, exact nature and the amount of each phosphor in composite coating can be changed according to the needs of terminal use.
Example
Example subsequently is only illustrative, and is not construed as any of the scope to claimed invention The restriction of species.
General procedure
Prepared by composite laminate sample
By making individually to gather（Methyl methacrylate）, i.e. PMMA（Aldrich）（By the molecule that GPC metering is 120000 Amount）With K2SiF6:Mn4+（PSF）Prepare two samples with YAG mixing.Make 300 microns（um）Screening 4.5 g PMMA with 2.5 g K2SiF6:Mn（5 mol% Mn, granular size 20 um）Combination, and, rescreening is carried out to mixture（300 um）, to prepare sample mixture 1.Make the 4.9 g PMMA and 0.59 g YAG of 150 um screenings（Aldrich）Combination, and, Rescreening is carried out to mixture（150 um）, to prepare sample mixture 2.In a vacuum chamber, to two sample mixtures It is not de-gassed and continue about 15 minutes.The mixture of sample 1 is poured into the disk of a diameter of 7.5 cm and 400 um thickness In shape mould, and, the mixture of sample 2 is poured into the disc mould of a diameter of 7.5 cm and 200 um thickness.Then, In a vacuum, 200oUnder C, under the pressure of 80 pounds/square inch, each mould containing mixture is pressed, after Face is 175oUnder C, under the pressure of 550 pounds/square inch, carry out framework pressing.Both press during, at a temperature of It is reduced to 70oAfter C, discharge pressure.Sample belt 1 containing PFS is of about that 410 um are thick, and, the sample belt 2 containing YAG It is of about that 205 um are thick.Two circular strip stack in the way of one on another, and, release film is positioned over this lamination Above and below.It is positioned over this lamination in vacuum lamination instrument, and be heated to 180 alwaysoC；Further, 80 pounds/flat Press under the pressure of side's inch, with by two band bondings.Then, under stress, this lamination is made to cool down.Obtained is compound Laminate is that about 615 um of the different area with YAG or PSF phosphor are thick,.
Luminous intensity is measured
By by composite laminate（As prepared above）It is arranged separately on blue LED die（Peak value at 450 nm is sent out Penetrate）, thus prepare two samples（Sample 1 and sample 2）.With the help of layer of silicone, composite laminate is adhered to LED core Piece.For sample 1, composite laminate is arranged in LED chip, wherein contains the side of PFS in LED chip（PFS to Under）, and, it for sample 2, is positioned over the surface containing YAG of composite laminate in LED chip（YAG is downward）.Fig. 4 shows Go out emission spectrum；Further, table 1 illustrates sample 1 and the spectral characteristic of sample 2.
Table 1
Sample CRI CCT CIE-x CIE-y DBB
Sample 1（PFS is downward） 92.8 2092 0.498 0.389 -0.026
Sample 2（YAG is downward） 77 2891 0.460 0.436 0.025
From measurement（Fig. 4 ＆ table 1）Being clearly, sample 1 has than sample 2 higher CRI significantly and lower CCT.
Although illustrating and describe only some feature of the present invention herein, but those skilled in the art are it is appreciated that many Modifications and variations.It is, therefore, to be understood that appended claims be intended to cover as fall within the true spirit of the invention all this Class modifications and variations.

Claims (20)

1., for making a process for LED illumination device, comprise to be arranged at composite coating on the surface of LED chip；Wherein, Described composite coating comprises：
First composite bed, the phosphor of the additive Mn of contained I and the first adhesive,
Ax[MFy]：Mn4+……（I）
Wherein,
A is Li, Na, K, Rb, Cs or a combination thereof；
M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof；
X is [MFy] absolute value of electric charge of ion；
Y is the 5th, 6 or 7；And
Second composite bed, comprises the second phosphor component and the second adhesive,
Wherein, described first adhesive, described second adhesive or both all comprise to gather（Methyl）Acrylate.
2. process as claimed in claim 1, wherein, by being arranged at described first composite bed on described second composite bed Form described composite coating.
3. process as claimed in claim 2, wherein, setting comprises that described first composite bed is bonded to described second and is combined Layer.
4. process as claimed in claim 3, wherein, by adhesive by described first composite bed and described second composite bed Bonding.
5. process as claimed in claim 1, wherein, before being arranged at described composite coating in described LED chip, makes institute State composite coating solidification.
6. process as claimed in claim 1, wherein, the phosphor of the described additive Mn of Formulas I comprises to have with from about 20 The particle population of the particle size distribution to the D50 value in the scope of about 50 microns for the micron.
7. process as claimed in claim 1, wherein, the phosphor of the described additive Mn of Formulas I comprises to have with from about 10 The particle population of the particle size distribution to the D50 value in the scope of about 30 microns for the micron.
8. process as claimed in claim 1, wherein, described first adhesive, described second adhesive or both all comprise with The particulate of the particle size distribution of the D50 value less than about 300 microns.
9. process as claimed in claim 8, wherein, described first adhesive, described second adhesive or both all comprise with The particulate of the particle size distribution of the D50 value from about 150 microns to about 300 microns.
10. process as claimed in claim 1, wherein, described first adhesive, described second adhesive or both all comprise with The particulate of the particle size distribution of the D50 value from about 20 microns to about 50 microns.
11. processes as claimed in claim 1, wherein, described poly-（Methyl）Acrylate is poly-（Methyl methacrylate）.
12. processes as claimed in claim 1, wherein, the phosphor of described additive Mn is K2SiF6:Mn4+.
13. 1 kinds of LED illumination device, comprise the composite coating being arranged on the surface of LED chip, and described composite coating comprises：
First composite bed, the phosphor of the additive Mn of contained I and the first adhesive,
Ax[MFy]：Mn4+……（I）
Wherein, A is Li, Na, K, Rb, Cs, NR4 or a combination thereof；M be Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof；R is H, low alkyl group or a combination thereof；X is [MFy] absolute value of electric charge of ion；And y is 5th, 6 or 7；And
Second composite bed, comprises the second phosphor component and the second adhesive,
Wherein, described first adhesive, described second adhesive or both all comprise to gather（Methyl）Acrylate.
14. LED illumination device as claimed in claim 13, wherein, the phosphor of described additive Mn is K2SiF6:Mn4+.
15. LED illumination device as claimed in claim 13, wherein, described poly-（Methyl）Acrylate is poly-（Methacrylic acid Methyl esters）.
16. LED illumination device as claimed in claim 13, wherein, the phosphor of described additive Mn comprises to have with from greatly The particle population of the particle size distribution of the D50 value in the scope of about 20 microns to about 50 microns.
17. LED illumination device as claimed in claim 13, wherein, the composite fluoride of the described additive Mn of Formulas I comprises to have Particle population with the particle size distribution of the D50 value in the scope from about 10 microns to about 30 microns.
18. LED illumination device as claimed in claim 13, wherein, described first composite bed is arranged at the institute of described LED chip State on surface, and, described second composite bed is arranged on the surface relative with described LED chip of described first composite bed.
19. LED illumination device as claimed in claim 13, wherein, described second composite bed is arranged at the institute of described LED chip State on surface, and, described first composite bed is arranged on the surface relative with described LED chip of described second composite bed.
20. LED illumination device as claimed in claim 13, wherein, described first composite bed has at the manganese across its thickness dense The classification composition of change in degree.
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